EP0540066B1 - Matériaux composite thermoplastique renforcé par des fibres, contenant des polyamides - Google Patents

Matériaux composite thermoplastique renforcé par des fibres, contenant des polyamides Download PDF

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Publication number
EP0540066B1
EP0540066B1 EP92122004A EP92122004A EP0540066B1 EP 0540066 B1 EP0540066 B1 EP 0540066B1 EP 92122004 A EP92122004 A EP 92122004A EP 92122004 A EP92122004 A EP 92122004A EP 0540066 B1 EP0540066 B1 EP 0540066B1
Authority
EP
European Patent Office
Prior art keywords
polyamide
composite materials
weight
thermoplastic
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92122004A
Other languages
German (de)
English (en)
Other versions
EP0540066A3 (en
EP0540066A2 (fr
Inventor
Heinz Dr. Horacek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PCD Polymere GmbH
Original Assignee
PCD Polymere GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PCD Polymere GmbH filed Critical PCD Polymere GmbH
Publication of EP0540066A2 publication Critical patent/EP0540066A2/fr
Publication of EP0540066A3 publication Critical patent/EP0540066A3/de
Application granted granted Critical
Publication of EP0540066B1 publication Critical patent/EP0540066B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the invention relates to thermoplastic fiber-reinforced composite materials which can be obtained by impregnating reinforcing fibers with a melt which is obtained from a mixture of thermoplastics, polyamides, anthranilic acid amide and, if appropriate, an adhesion promoter, a process for producing these composite materials and their use.
  • Fiber-reinforced thermoplastics are valuable construction materials, especially in machine and apparatus construction. Such plastics are known, for example, from DE-PS 29 48 235. A disadvantage of these plastics, however, is that their mechanical properties, in particular strength and modulus, are no longer sufficient, especially in more demanding applications. Another disadvantage is their sometimes difficult processing, in particular in the case of thermoplastics with higher temperature resistance, which is particularly evident in the difficult impregnation of the reinforcing fibers, for example glass fiber mats, with these high-temperature-resistant thermoplastic melts from US Pat. No.
  • polyamide-polyphenylene ether mixtures An improvement in the impact strength of polyamide-polyphenylene ether mixtures is achieved according to EP-A-0 234 060 by adding esters of trihydric to hexavalent alcohols and aliphatic carboxylic acids.
  • this mixture can additionally contain liquid diene polymers, epoxides, unsaturated carboxylic acids or their derivatives, aliphatic polycarboxylic acids, silanes, functionalized polyphenylene ethers, oxidized polyolefin waxes, copolymers of dicarboxylic acids and vinylaromatic compounds.
  • surfactants, soaps, modified rubbers or epoxides are added to the polyamide-polyphenylene ether mixture according to EP-A-0 270 247, with rubbers, epoxides and unsaturated carboxylic acids or their derivatives being preferred.
  • an ethylene-propylene rubber grafted with maleic anhydride is used.
  • WO 85/05372 describes thermoplastic, fiber-reinforced composite materials which are produced from a mixture of polyphenylene ether, polyamide, glass fiber and a polycarboxylic acid or its ester- or N-substituted amide derivatives.
  • the object of the present invention was to find fiber-reinforced thermoplastics with improved mechanical properties and good processability.
  • the invention accordingly relates to a thermoplastic fiber-reinforced composite material which can be obtained by impregnating reinforcing fibers with the melt of a mixture which contains 10 to 90 parts by weight of thermoplastic, 90 to 10 parts by weight of polyamide and optionally 1 to 10 parts by weight of coupling agent , the mixture additionally containing 0.1 to 10% by weight, based on the amount of polyamide, of anthranilic acid amide.
  • thermoplastics which can be used for the production of fiber-reinforced plastics can be used as thermoplastics, for example those such as those mentioned in DE-PS 29 48 235.
  • Possible thermoplastics are e.g. B. polyolefins, polyamides, polyimides, polysulfones, polyacetals, polycarbonates, polystyrene, acrylic resins, polyesters, polyetherimides, polyether sulfones, polyether ketones, polyether ether ketones, polyphenylene ethers, polyphenylene sulfide and polytetrafluoroethylene, and mixtures of these thermoplastics.
  • Suitable polyamides are, for example, those as stated in EP-A 221 341 or EP-A 225 170, polyamide 6 or polyamide 6.6 are preferably used.
  • Further examples of polyamides (PA) are poly-4-aminobutyric acid (PA 4), poly-7-aminoheptanoic acid (PA 7), poly-8-aminoctanoic acid (PA 8), poly-10-aminodecanoic acid (PA 10), poly 11-aminoundecanoic acid (PA 11), poly-12-aminododecanoic acid (PA 12), polyheptamethylene pimelamide (PA 7.7), polyocta methylene suberamide (PA 8.8), polyhexamethylene sebacamide (PA 6.10), polynonamethylene acelamide (PA 9.9) , Polydecamethylene acelamide (PA 10.9), polydecamethylene sebacamide (PA 10.10), polybis (4-aminocyclohexyl) methane 1.10 decanedicarboxamide, poly (
  • the addition of the acid amide brings about a reduction in the melt viscosity which is proportional to the amount of the acid amide added, which enables better impregnation and thus improves the mechanical properties of the composites.
  • the polymer mixture for impregnating the reinforcing fibers preferably contains 0.5 to 5% acid amide, based on the amount of the polyamide.
  • Suitable adhesion promoters can bring about a further improvement in the mechanical properties of various polyamide-thermoplastic mixtures.
  • Suitable adhesion promoters are, for example, block copolymers of polyamide and the thermoplastic in question, or polyolefins with functional groups, such as. B. carboxyl or hydroxyl groups.
  • the production of such block copolymers is, for example, according to J. Pol. Sci., Pol. Chem. Ed. 17 (1979) pp. 2317 - 2335 by reacting polyamide blocks containing amino end groups with polyphenylene ether or polyphenylene sulfide blocks and hexamethylene diisocyanate containing hydroxyl or thiol end groups.
  • Such block copolymers are also commercially available, for example Pebax (R) from Atochem, a polyamide-polyether block copolymer.
  • the commercially available Bynel (R) CXA 3101 from Du Pont is a copolymer of ethylene with monomers containing carboxyl or hydroxyl groups.
  • the mixture for impregnating the reinforcing fibers preferably contains 40 to 60 parts by weight of thermoplastic and 60 to 40 parts by weight of polyamide.
  • composite materials which can be obtained by impregnating the reinforcing fibers by hot pressing at temperatures from 10 to 200 ° C. above the melting point of the melt and at pressures from 1.2 to 40 bar.
  • reinforcing fibers are all known fibers usable for reinforced plastics, such as. B. fibers of glass, carbon, aramid, ceramic, metal or mixtures thereof. Fibers are to be understood as both cut fibers and continuous fibers, for example in the form of unidirectional rovings, and also fabrics and fiber mats, which can also consist of cut fibers or continuous fibers.
  • the finished composite usually has a reinforcing fiber content of approximately 15 to 60% by volume.
  • Another object of the invention is the production of the composite materials according to the invention. It is carried out by melting a mixture of 10 to 90 parts by weight of one or more thermoplastics and 90 to 10 parts by weight of one or more polyamides and optionally 1 to 10 parts by weight of adhesion promoter, this mixture being 0.1 to 10% by weight, based on the amount of polyamide, contains anthranilic acid amide.
  • the reinforcing fibers are impregnated with this melt at temperatures 10 to 200 ° C. above the melting point of the melt.
  • Fiber mats, fabrics or rovings made from continuous fibers can be impregnated, for example, by means of pultrusion.
  • rovings either individual roving strands or a plurality of roving strands placed next to one another in a band can be pulled through the melt and then cooled after calibration for solidification.
  • the reinforcing fibers are impregnated by being pressed together with the melt in a hot press at temperatures from 10 to 200 ° C. above the melting point of the melt and at pressures from 1.2 to 40 bar.
  • a continuous press is particularly preferably used, to which the mixture of thermoplastics, polyamides, acid amides and, if appropriate, adhesion promoter is fed either in the form of a prefabricated film or as a freshly extruded melt together with one or more fiber mats, fabrics or unidirectional roving strands.
  • the composite is also cooled and solidified in a subsequent cooling zone under pressure.
  • the fiber-reinforced polymer strands can be cut into granules, which can be further processed, for example by injection molding or extrusion, into finished parts.
  • the composite materials in the form of sheets or plates can be used as a starting material for the production of molded parts by hot pressing.
  • the sheets or plates heated to about 10 to 200 ° C. above the melting point of the polymer mixture used are placed in heated molds and pressed at temperatures of about 50 to 120 ° C. and pressures of 1 to 100 bar.
  • the melt film was pressed continuously on a double belt press at 250 ° C. and 5 bar with 2 glass mats (Syncomat, each 650 g / m 2 ).
  • Table 1 also shows the corresponding values known from EP-A-369 313 for an analog mixture or combination, but which have no anthranilic acid amide content.
  • Table 1 with 2% AN without AN MFI (g / 10 min) 260 18th Tensile strength (N / mm 2 ) 150 70 Strain (%) 2.5 3.5 Impact strength (kJ / m 2 ) 60 50 Bending modulus of elasticity (N / mm 2 ) 7000 6000

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Claims (10)

  1. Procédé de fabrication de matériaux composites thermoplastiques renforcés avec des fibres, caractérisé en ce qu'on fait fondre un mélange de 10 à 90 parties en poids de matière thermoplastique, 90 à 10 parties en poids de polyamide et éventuellement 1 à 10 parties en poids d'agent adhésif, ce mélange contenant de 0,1 à 10 % en poids d'amide d'acide anthranilique, par rapport à la quantité de polyamide, et on imprègne des fibres de renfort avec cette masse fondue.
  2. Procédé de fabrication de matériaux composites selon la revendication 1, caractérisé en ce que ces matériaux composites possèdent une résistance au thermoformage d'au moins 145°C, mesurée avec l'aiguille de Vicat d'après la norme DIN 53460.
  3. Procédé de fabrication de matériaux composites selon la revendication 1 ou 2, caractérisé en ce que le mélange servant à l'imprégnation des fibres de renfort contient de 0,5 à 5 % d'amide d'acide anthranilique par rapport à la quantité de polyamide.
  4. Procédé de fabrication de matériaux composites selon l'une des revendications 1 à 3, caractérisé en ce que le mélange servant à l'imprégnation des fibres de renfort contient de 40 à 60 parties en poids de matière thermoplastique et 60 à 40 parties en poids de polyamide.
  5. Procédé de fabrication de matériaux composites selon l'une des revendications 1 à 4, caractérisé en ce qu'on effectue l'imprégnation par compression conjointe des fibres de renfort avec le mélange de matière thermoplastique, de polyamide, d'amide d'acide anthranilique et éventuellement d'agent adhésif, à des températures de 10 à 200°C au-dessus du point de fusion de la masse fondue et à des pressions de 1,2 à 40 bars.
  6. Procédé de fabrication de matériaux composites selon la revendication 5, caractérisé en ce qu'on utilise le mélange de matière thermoplastique, de polyamide, d'amide d'acide anthranilique et éventuellement d'agent adhésif sous la forme d'un film préfabriqué ou d'un film de matière fondue fraîchement extrudée et on l'amène dans une presse à régime continu en même temps que les fibres de renfort qui se présentent sous la forme d'une nappe ou sous la forme de brins unidirectionnels de fibres sans fin.
  7. Utilisation des matériaux composites selon l'une des revendications 1 à 6 comme matériau de départ pour la fabrication d'éléments moulés par compression à chaud.
  8. Utilisation des matériaux composites selon l'une des revendications 1 à 6 comme matériau de départ pour la fabrication de granules.
EP92122004A 1988-11-15 1989-11-08 Matériaux composite thermoplastique renforcé par des fibres, contenant des polyamides Expired - Lifetime EP0540066B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT2790/88A AT393126B (de) 1988-11-15 1988-11-15 Thermoplastischer faserverstaerkter verbundwerkstoff mit einem gehalt an polyamiden, verfahren zu seiner herstellung und seine verwendung
AT2790/88 1988-11-15
EP89120693A EP0369312B1 (fr) 1988-11-15 1989-11-08 Matériau composite thermoplastique renforcé par des fibres, contenant des polyamides

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP89120693.0 Division 1989-11-08

Publications (3)

Publication Number Publication Date
EP0540066A2 EP0540066A2 (fr) 1993-05-05
EP0540066A3 EP0540066A3 (en) 1993-06-30
EP0540066B1 true EP0540066B1 (fr) 1996-09-04

Family

ID=3540325

Family Applications (2)

Application Number Title Priority Date Filing Date
EP89120693A Expired - Lifetime EP0369312B1 (fr) 1988-11-15 1989-11-08 Matériau composite thermoplastique renforcé par des fibres, contenant des polyamides
EP92122004A Expired - Lifetime EP0540066B1 (fr) 1988-11-15 1989-11-08 Matériaux composite thermoplastique renforcé par des fibres, contenant des polyamides

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP89120693A Expired - Lifetime EP0369312B1 (fr) 1988-11-15 1989-11-08 Matériau composite thermoplastique renforcé par des fibres, contenant des polyamides

Country Status (4)

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EP (2) EP0369312B1 (fr)
AT (3) AT393126B (fr)
DE (2) DE58909722D1 (fr)
ES (2) ES2090472T3 (fr)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1985005372A1 (fr) * 1984-05-21 1985-12-05 General Electric Company Compositions a base de polyamide - ether de polyphenylene modifies et procede
NL8600167A (nl) * 1986-01-27 1987-08-17 Gen Electric Polymeermengsel met polyfenyleenether en polyamide.
US4749736A (en) * 1986-10-20 1988-06-07 Allied Corporation Nucleating system for polyamides
JP2514051B2 (ja) * 1986-10-31 1996-07-10 住友化学工業株式会社 熱可塑性樹脂組成物
AT393127B (de) * 1988-11-15 1991-08-26 Danutec Werkstoff Thermoplastischer faserverstaerkter verbundwerkstoff aus polyphenylenethern und polyamiden, verfahren zu seiner herstellung und seine verwendung

Also Published As

Publication number Publication date
EP0369312B1 (fr) 1993-12-29
EP0540066A3 (en) 1993-06-30
ATE142237T1 (de) 1996-09-15
ES2060724T3 (es) 1994-12-01
ATE99346T1 (de) 1994-01-15
EP0369312A1 (fr) 1990-05-23
ATA279088A (de) 1991-01-15
DE58906575D1 (de) 1994-02-10
EP0540066A2 (fr) 1993-05-05
AT393126B (de) 1991-08-26
ES2090472T3 (es) 1996-10-16
DE58909722D1 (de) 1996-10-10

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